Process for manufacturing ortho-amino-arylmercaptanes



Patented Dec. 9, 1930 UNITED. STATES RIoHA D HERZ, E FRANKFORT-ON'-THE-MAIN,- AND MAX scnUBER'r, 0E EEGHENHEIM, NEAR E ANxEoRr-oN rHE-MAIN, GERMANY," ASSIGNORS TO GENERAL ANILINE WORKs, me, on NEW YoRK, N. Y., A CORPORATION 0E DELAWARE PROCESS FOR MANUFACTURING ORTIIO-AMINOARYLMERCAPTANES No Drawing. Application filedMarchQl, 1928, Serial No. 263,584, and in Germany March 26, 1927.

We have found an almost generally applicable method for producing ortho-aminoarylmercaptanes of the general formula:

wherein Y means that the 4-position is either substituted or blockaded. ()ur process consistsin treating ortho-aminoaryl-sulfocyanogen compounds of the general formula:

(4) Y ary1 SGN (2) I,

wherein Y has the aforesaid signification, obtainable e. g. by causing an inorganic sulfocyanic salt and a halogen to act on a primary aromatic amine having the para-position to the amino group blocked in the presence of a solvent of a neutral character, with alkaline saponifying agents, under-exclusion of air, preferably inthe presence of a reducing agent. Advantageously alkaline acting agents having simultaneously a re ducing effect as for instance an aqueous or alcoholic solution of alkali sulfides or polysulfides may be used for our process.

The ortho-aminoarylmercaptanes, thus obtained in a smooth reaction have all characteristic properties of this class of intermediates for the production of dyestulfs of the thioindigo series, particularly they form with solutions of salts of heavy metals diflicultly soluble mercaptides and yield in a smooth reaction the corresponding ortho-aminoaryl- .thioglycolic acids when condensed with 'monochloroacetic acid. Advantageously one may directly use for this latter condensation the alkaline solutions of the mercapto compounds obtained according to our process without isolating the mercapto-compounds themselves.

understood that we are not limited to the products nor reaction conditions mentioned therein.

Example 1 40parts of 1-methyl-2-amino-3-sulfocyanogen-5-chloro-benzene, obtained eig. by the 4 action of potassium sulfocyanide and bromine on 1-methyl-2-amino-5-chloro-benzene in the presence of methylalcohol, are suspended in 400 parts of spirit and mixed with 140 parts of a dilute caustic soda solution containing 24 parts of sodium hydroxide, advantageously with addition of parts of sodium hydrosulfite or the equivalent amount of zinc dust. Then the mass is warmed for a short time while stirring. WVhen the reaction is finished, the spirit is advantageously dis tilled off. The residual aqueous solution contains the 1-methyl-2-amino-5 chloro-benzene- 3-merc-aptane of the formula:

C1- SE in the form of its sodium salt. In order to obtain it in a stable state it may be precipitated therefrom in the usual manner as the difficulty soluble zinc mercaptide by the addition of a soluble zinc salt. In order to ch'loro benzene 3 thioglycolic acid corresponding to the formula:

01 someoon is formed which is advantageously isolated in the form of its inner anhydride melting at about 186.

The saponification of the sulfocyanogen compound may be carried out with the same result by means of an aqueous or alcoholic solution of alkali sulfides or polysulfides.

Example 2 40 parts 'of' 1-amino-2-sulfocyanogen 4 ethoxy-benzene, obtainable e. g. according to PATENTAOFFICEu i the above mentioned process by starting from V paraphenetidine, are introduced into a solution of 32 parts'of sodium sulfide and 8 parts of sulfur in 200 to 300 parts of spirit and the mass isboiled under a reflux condenser for a shortctime... lihen the'spirit distilled of, the residue is dissolved 1n 500 parts Of water and precipitated by addition of an 40, is obtained. condensation with mono-v chloio-acetic ,acid it is converted intothe the formula:

acidto'the solution, --For purifying the precipitate may bered-issolved in a dilute caustic soda solution, advantageously with addition of a small quantity of a'reducing agent, and the solution is separated from'the remaining sulfur by filtration. This solution contains the I-amino-4-eth oxybenZene-2-mercaptai1e of ;the formula:

forniof its sodium salt and yields when condensedT'with; monochloroacetic acidv according to Example 1 the lan1ino-4-ethoxy-. 'benzene-2-thiogl colic acid. The mercapto-f com oundamay e'isolated" as its diilicultly solu le'zincmercaptide Example}? i V when startingffrom 40 parts of ll-sulfocyanogen 2 aminognaphthalene obtainable e. g. according to the above mentioned process by startin from'beta-naphthylamine and working ot erwise as described in Example 1, the 2-aminonaphthalenel mercaptane of 2-amino-naphthalene-1-thi0glycolic acid. I

We claim: I i

1. A' process for manufacturing orth'o- I .amino-arylmercaptans treating an 'orthowamino aryl-sulfocyanogen which comprises compound of the generalformula i.

L wherein Y means that tne i-position iseither I r substituted or blockaded with an alkaline 7 I NH: 4) Ya.ryl soN a saponifyingagent under exclusion of air.

25A process for manufacturing orthoamino-.arylmercaptans :which treating an 'ortho-amino-aryl-sulfocyanogeni comprises compound of the general formula:

( I w y SCN (2V) wherein Y means that the 1-position is either substituted or blockaded with an alkaline saponifying agent with the addition of a re- .ducing agent. i

"a reducing. actlon.

"amino-aryl-mercaptjans I natures. p

3. A process for manufacturing orthoamino arylmercaptans which comprises. treating an ortho-amino-aryl-sulfocyanogen compoundof the general formula:

(Q Y'PN'YKSON wherein (Y means that the 4- position is either substituted or blockaded with an alkaline;

,NH, 7 V

1 Y on,

V wherein Y means a monovalent substituent i and the benzene nucleus may contain further asubstituentsewith an alkaline saponifying agentunder exclusion of air.

5. A process for manufacturlng ortho-.- amino-.aryl-mercaptans which comprises treating an ortho-amino-aryl-sulfocyanogen compound of the genefral 'formula:

wherein X means alkyl and Y means alkoxyforhalo en, with an alkaline saponifying agent un er exclusion of airfu,v

6. A process for manufacturing-l-methyle an alkaline saponifying t u r exclusion of air.

'saponifyingagentbeingcapableof Q-amino 5-chloro-benzene-3-inercaptan which f a comprise'streating 1-methyl-2-amino-3-sul-- 1 focya-nogen 5chloro-henzene of the formula:

: v ,4 y Y a In testimony :whereof, we affix our sig 7 I RIG'HARDH'E'RZ, M X SCHUBERT; 

